JP2012116800A - Aromatic sulfonic acid derivative and method for producing the same - Google Patents
Aromatic sulfonic acid derivative and method for producing the same Download PDFInfo
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- -1 Aromatic sulfonic acid derivative Chemical class 0.000 title claims abstract description 48
- 238000004519 manufacturing process Methods 0.000 title claims description 13
- 125000003118 aryl group Chemical group 0.000 claims abstract description 27
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 7
- 150000001342 alkaline earth metals Chemical group 0.000 claims abstract description 7
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 6
- 150000001340 alkali metals Chemical group 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 46
- 239000007795 chemical reaction product Substances 0.000 claims description 15
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 14
- 125000005843 halogen group Chemical group 0.000 claims description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 9
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims description 9
- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 7
- 150000001491 aromatic compounds Chemical class 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 230000002829 reductive effect Effects 0.000 claims description 2
- 239000002861 polymer material Substances 0.000 abstract description 24
- 239000000178 monomer Substances 0.000 abstract description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 4
- 239000001257 hydrogen Substances 0.000 abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 3
- 239000004215 Carbon black (E152) Substances 0.000 abstract 1
- 229910052736 halogen Inorganic materials 0.000 abstract 1
- 150000002367 halogens Chemical class 0.000 abstract 1
- 229930195733 hydrocarbon Natural products 0.000 abstract 1
- 150000002431 hydrogen Chemical group 0.000 abstract 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 14
- 239000002904 solvent Substances 0.000 description 13
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 7
- 239000005518 polymer electrolyte Substances 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 239000012528 membrane Substances 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 238000006277 sulfonation reaction Methods 0.000 description 6
- 238000006722 reduction reaction Methods 0.000 description 5
- QYXHDJJYVDLECA-UHFFFAOYSA-N 2,5-diphenylcyclohexa-2,5-diene-1,4-dione Chemical compound O=C1C=C(C=2C=CC=CC=2)C(=O)C=C1C1=CC=CC=C1 QYXHDJJYVDLECA-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 239000000446 fuel Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 3
- 125000002529 biphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C12)* 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 125000001153 fluoro group Chemical group F* 0.000 description 3
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 125000004957 naphthylene group Chemical group 0.000 description 3
- 239000012488 sample solution Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 125000005074 adamantylmethyl group Chemical group 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 125000004210 cyclohexylmethyl group Chemical group [H]C([H])(*)C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C1([H])[H] 0.000 description 2
- 125000004851 cyclopentylmethyl group Chemical group C1(CCCC1)C* 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 description 1
- 229940005561 1,4-benzoquinone Drugs 0.000 description 1
- PLVUIVUKKJTSDM-UHFFFAOYSA-N 1-fluoro-4-(4-fluorophenyl)sulfonylbenzene Chemical compound C1=CC(F)=CC=C1S(=O)(=O)C1=CC=C(F)C=C1 PLVUIVUKKJTSDM-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- GKPHNZYMLJPYJJ-UHFFFAOYSA-N 2,3-difluorobenzonitrile Chemical compound FC1=CC=CC(C#N)=C1F GKPHNZYMLJPYJJ-UHFFFAOYSA-N 0.000 description 1
- YOYAIZYFCNQIRF-UHFFFAOYSA-N 2,6-dichlorobenzonitrile Chemical compound ClC1=CC=CC(Cl)=C1C#N YOYAIZYFCNQIRF-UHFFFAOYSA-N 0.000 description 1
- BNBRIFIJRKJGEI-UHFFFAOYSA-N 2,6-difluorobenzonitrile Chemical compound FC1=CC=CC(F)=C1C#N BNBRIFIJRKJGEI-UHFFFAOYSA-N 0.000 description 1
- SMDLELADPFDJCZ-UHFFFAOYSA-N 2,6-diphenylcyclohexa-2,5-diene-1,4-dione Chemical compound C=1C(=O)C=C(C=2C=CC=CC=2)C(=O)C=1C1=CC=CC=C1 SMDLELADPFDJCZ-UHFFFAOYSA-N 0.000 description 1
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 1
- GPAPPPVRLPGFEQ-UHFFFAOYSA-N 4,4'-dichlorodiphenyl sulfone Chemical compound C1=CC(Cl)=CC=C1S(=O)(=O)C1=CC=C(Cl)C=C1 GPAPPPVRLPGFEQ-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical group [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical group [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical group [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000000712 assembly Effects 0.000 description 1
- 238000000429 assembly Methods 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 150000007514 bases Chemical class 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 150000002221 fluorine Chemical class 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 150000002641 lithium Chemical group 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Chemical compound [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- 125000006551 perfluoro alkylene group Chemical group 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000005185 salting out Methods 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 125000004436 sodium atom Chemical group 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 125000001273 sulfonato group Chemical class [O-]S(*)(=O)=O 0.000 description 1
- 150000003458 sulfonic acid derivatives Chemical class 0.000 description 1
- HIFJUMGIHIZEPX-UHFFFAOYSA-N sulfuric acid;sulfur trioxide Chemical compound O=S(=O)=O.OS(O)(=O)=O HIFJUMGIHIZEPX-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Conductive Materials (AREA)
Abstract
Description
本発明は、フェニレン結合を有する芳香族スルホン酸誘導体、およびその製造方法に関するものである。 The present invention relates to an aromatic sulfonic acid derivative having a phenylene bond and a method for producing the same.
固体高分子型燃料電池は、燃料として純水素ガス、改質水素ガス、メタノールを用いるいずれの型でも、高分子電解質を２枚の電極で挟んだ膜電極接合体を複数積層したスタックと呼ばれるもので構成されている。高分子電解質膜には、出力の向上や燃料の有効利用の点から、プロトン伝導性に優れていることが求められる。 A polymer electrolyte fuel cell is a stack in which a plurality of membrane electrode assemblies in which a polymer electrolyte is sandwiched between two electrodes are used in any type that uses pure hydrogen gas, reformed hydrogen gas, and methanol as fuel. It consists of The polymer electrolyte membrane is required to be excellent in proton conductivity from the viewpoint of improvement in output and effective use of fuel.
高分子電解質膜の作製には、従来、パーフルオロアルキレン基を主鎖骨格とし、側鎖にスルホン酸基を有する高分子材料（フッ素系高分子材料）が用いられてきた。しかし、このフッ素系高分子材料は８０℃付近に軟化点を有することから、かかる高分子材料を用いて作製される高分子電解質膜は１００℃を超える高温下で使用することができなかった。 For the production of a polymer electrolyte membrane, conventionally, a polymer material (fluorine polymer material) having a perfluoroalkylene group as a main chain skeleton and a sulfonic acid group in a side chain has been used. However, since this fluorine-based polymer material has a softening point near 80 ° C., a polymer electrolyte membrane produced using such a polymer material could not be used at a high temperature exceeding 100 ° C.
そこで、高温下でも使用できる高分子電解質膜を提供するべく、フェニレン基を主鎖骨格とし、側鎖にスルホン酸基を有する高分子材料（芳香族系高分子材料）が検討されている(例えば、特許文献１)。しかしながら、従来の芳香族系高分子材料では、フェニレン基を主鎖骨格とするポリマーに対してスルホン酸基の導入がなされるため、スルホン化の部位がポリマーの化学構造の影響を受けることとなり、スルホン化率を十分に上げることができなかった。 Therefore, in order to provide a polymer electrolyte membrane that can be used even at high temperatures, a polymer material (aromatic polymer material) having a phenylene group as a main chain skeleton and a sulfonic acid group in a side chain has been studied (for example, Patent Document 1). However, in the conventional aromatic polymer material, since a sulfonic acid group is introduced into a polymer having a phenylene group as a main chain skeleton, the sulfonation site is affected by the chemical structure of the polymer. The sulfonation rate could not be increased sufficiently.
本発明者らは、プロトン伝導性に優れる芳香族系高分子材料、および該高分子材料を得るためのモノマーを提供することを課題として掲げた。 The present inventors raised as an object to provide an aromatic polymer material excellent in proton conductivity and a monomer for obtaining the polymer material.
本発明者らは、上記課題を解決すべく鋭意研究を行った。その結果、以下のフェニレン結合を有する芳香族スルホン酸誘導体をモノマー成分として用いることにより、上記課題を解決できることを見出し、本発明を完成するに至った。 The present inventors have intensively studied to solve the above problems. As a result, it has been found that the above problems can be solved by using an aromatic sulfonic acid derivative having the following phenylene bond as a monomer component, and the present invention has been completed.
すなわち、本発明にかかる芳香族スルホン酸誘導体は式（１）で表されることを特徴とする。 That is, the aromatic sulfonic acid derivative according to the present invention is represented by the formula (1).
[式（１）において、Ｘ１およびＸ２はそれぞれ独立した水素原子またはハロゲン原子を示す。Ｒは水素原子、アルカリ金属原子、アルカリ土類金属原子、または炭素数１〜２０の炭化水素基、ａおよびｂはそれぞれ独立した１以上の整数、Ａｒ１およびＡｒ２は独立した芳香族基を示す。] [In Formula (1), X 1 and X 2 each independently represent a hydrogen atom or a halogen atom. R represents a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, or a hydrocarbon group having 1 to 20 carbon atoms, a and b each represent an independent integer of 1 or more, and Ar 1 and Ar 2 represent an independent aromatic group. Show. ]
本発明において、下記式（１）におけるＡｒ１およびＡｒ２がフェニレン基であることが好ましい実施態様である。 In the present invention, Ar 1 and Ar 2 in the following formula (1) are preferably phenylene groups.
また、本発明には、前記芳香族スルホン酸誘導体の製造方法であって、下記式（２）で表される芳香族化合物から、還元反応にて水酸基を生成する第一反応工程と、第一反応工程で得られる反応精製物をスルホン化する第二反応工程とを含むことを特徴とする製造方法も包含される。 The present invention also provides a method for producing the aromatic sulfonic acid derivative, comprising a first reaction step of generating a hydroxyl group by a reduction reaction from an aromatic compound represented by the following formula (2): And a second reaction step of sulfonating the purified reaction product obtained in the reaction step.
[式（２）において、Ｘ１およびＸ２はそれぞれ独立した水素原子またはハロゲン原子を示す。] [In Formula (2), X 1 and X 2 each independently represent a hydrogen atom or a halogen atom. ]
上記製造方法において、前記第一反応工程を、反応温度−２０℃〜２００℃、前記反応生成物の濃度を１質量％〜１０質量％となるように行うことや、前記第二反応工程を、反応温度０℃〜１００℃で行うこと、および前記反応生成物に対して２当量〜２０当量の硫酸を加えて行うことが好ましい実施態様である。 In the said manufacturing method, said 1st reaction process is performed so that reaction temperature may be -20 degreeC-200 degreeC, and the density | concentration of the said reaction product may be 1 mass%-10 mass%, said 2nd reaction process, It is a preferred embodiment that the reaction is carried out at a reaction temperature of 0 ° C. to 100 ° C. and 2 to 20 equivalents of sulfuric acid is added to the reaction product.
本発明にかかる芳香族スルホン酸誘導体は、２個以上のスルホン酸基を有している。このため、当該誘導体をモノマー成分として用いることにより、スルホン化率の高い芳香族系高分子材料を得ることができ、ひいてはプロトン伝導性に優れた高分子電解質膜を提供できるものと推察される。 The aromatic sulfonic acid derivative according to the present invention has two or more sulfonic acid groups. For this reason, it is speculated that by using the derivative as a monomer component, an aromatic polymer material having a high sulfonation rate can be obtained, and as a result, a polymer electrolyte membrane excellent in proton conductivity can be provided.
また、当該芳香族系高分子材料は、スルホン酸基が剛直性の高い側鎖（芳香族基）に導入されているため、スルホン酸基を多量に導入したことに起因する耐熱水性や機械的特性の低下が起こり難いと推察される。 In addition, since the aromatic polymer material has a sulfonic acid group introduced into a highly rigid side chain (aromatic group), it is resistant to hot water and mechanical properties caused by the introduction of a large amount of the sulfonic acid group. It is inferred that the characteristics are unlikely to deteriorate.
本発明の芳香族スルホン酸誘導体は式（１）で表されることを特徴とする。 The aromatic sulfonic acid derivative of the present invention is represented by the formula (1).
[式（１）において、Ｘ１およびＸ２はそれぞれ独立した水素原子またはハロゲン原子を示す。Ｒは水素原子、アルカリ金属原子、アルカリ土類金属原子、または炭素数１〜２０の炭化水素基、ａおよびｂはそれぞれ独立した１以上の整数、Ａｒ１およびＡｒ２は独立した芳香族基を示す。] [In Formula (1), X 1 and X 2 each independently represent a hydrogen atom or a halogen atom. R represents a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, or a hydrocarbon group having 1 to 20 carbon atoms, a and b each represent an independent integer of 1 or more, and Ar 1 and Ar 2 represent an independent aromatic group. Show. ]
以下、当該芳香族スルホン酸誘導体の詳細、およびその製造方法について説明する。 Hereafter, the detail of the said aromatic sulfonic acid derivative and its manufacturing method are demonstrated.
（芳香族スルホン酸誘導体）
式（１）における構成の、当該誘導体をモノマー成分として用いて重合させて芳香族系高分子材料を調製する際に、当該ＯＨで表される水酸基部位が反応し、主鎖骨格を構成するため、スルホン酸基は側鎖に配されることとなる。
(Aromatic sulfonic acid derivatives)
When preparing an aromatic polymer material by polymerizing the derivative of the structure of formula (1) as a monomer component, the hydroxyl group represented by the OH reacts to form the main chain skeleton. The sulfonic acid group is arranged in the side chain.
Ｘ１およびＸ２のハロゲン原子は、特に限定されるものではなく、例えばフッ素原子、塩素原子、臭素原子、ヨウ素原子が挙げられる。 Halogen atom of X 1 and X 2 are not particularly limited, for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom.
式（１）中、Ｒで表されるアルカリ金属原子、アルカリ土類金属原子としては、特に限定されるものではなく、アルカリ金属原子としては、例えばリチウム原子、ナトリウム原子、カリウム原子等が挙げられる。またアルカリ土類金属原子としては、例えばマグネシウム原子やカルシウム原子等が挙げられる。なお、Ｒがアルカリ土類金属原子である場合には、かかる金属原子は芳香族スルホン酸誘導体中の複数のスルホン酸基と塩を形成していてもよい。あるいは、芳香族スルホン酸誘導体中のスルホン酸基、および塩化物イオン、硝酸イオン、過塩素酸イオンなどの遊離イオンの両方と塩を形成してもよい。 In formula (1), the alkali metal atom and alkaline earth metal atom represented by R are not particularly limited, and examples of the alkali metal atom include a lithium atom, a sodium atom, and a potassium atom. . Examples of the alkaline earth metal atom include a magnesium atom and a calcium atom. When R is an alkaline earth metal atom, the metal atom may form a salt with a plurality of sulfonic acid groups in the aromatic sulfonic acid derivative. Alternatively, a salt may be formed with both the sulfonic acid group in the aromatic sulfonic acid derivative and free ions such as chloride ion, nitrate ion and perchlorate ion.
また、Ｒで表される炭素数１〜２０の炭化水素基としては、特に限定されるものではないが、メチル基、エチル基、プロピル基、ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基等の直鎖状炭化水素基；イソプロピル基、イソブチル基、ｔ−ブチル基、ｓ−ブチル基、イソペンチル基、ネオペンチル基、２−エチルヘキシル基、２-メチルブチル基等の分岐状炭化水素基；シクロペンチル基、シクロヘキシル基、シクロペンチルメチル基、シクロヘキシルメチル基、アダマンチル基、アダマンチルメチル基、テトラヒドロフルフリル基、３，３−ジメチル−２，４−ジオキソランメチル基、ビシクロ［２．２．２］ヘプチル基、ビシクロ［２．２．１］ヘプチルメチル基等の脂環式炭化水素基等が挙げられる。これらの炭化水素基の中でも、ネオペンチル基、シクロペンチルメチル基、シクロヘキシルメチル基、アダマンチルメチル基、テトラヒドロフルフリル基、ビシクロ［２．２．２］ヘプチル基が好ましい。 The hydrocarbon group having 1 to 20 carbon atoms represented by R is not particularly limited, but is a methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group. A linear hydrocarbon group such as a group; branched hydrocarbon groups such as isopropyl group, isobutyl group, t-butyl group, s-butyl group, isopentyl group, neopentyl group, 2-ethylhexyl group, and 2-methylbutyl group; cyclopentyl Group, cyclohexyl group, cyclopentylmethyl group, cyclohexylmethyl group, adamantyl group, adamantylmethyl group, tetrahydrofurfuryl group, 3,3-dimethyl-2,4-dioxolanemethyl group, bicyclo [2.2.2] heptyl group, And alicyclic hydrocarbon groups such as a bicyclo [2.2.1] heptylmethyl group. Among these hydrocarbon groups, a neopentyl group, cyclopentylmethyl group, cyclohexylmethyl group, adamantylmethyl group, tetrahydrofurfuryl group, and bicyclo [2.2.2] heptyl group are preferable.
式（１）中のａおよびｂは、それぞれ独立した１以上の整数を示し、その上限はＡｒ１およびＡｒ２の種類に応じて変動するものであるが、１または２であることが好ましい。ａおよびｂが３を超えると、合成時の収率が低下するなどの問題が生じる場合がある。 A and b in the formula (1) each independently represent an integer of 1 or more, and the upper limit thereof varies depending on the types of Ar 1 and Ar 2 , but is preferably 1 or 2. When a and b exceed 3, problems such as a decrease in yield during synthesis may occur.
式（１）中、Ａｒ１およびＡｒ２で表される芳香族基としては特に限定されるものではなく、例えば、フェニレン基、ナフチレン基、ビフェニレン基等が挙げられ、Ａｒ１とＡｒ２は同種であっても異種であってもよいが、Ａｒ１およびＡｒ２がともにフェニレン基であることが好ましい。 In the formula (1), the aromatic group represented by Ar 1 and Ar 2 is not particularly limited, and examples thereof include a phenylene group, a naphthylene group, a biphenylene group, and the like, and Ar 1 and Ar 2 are the same type. Or Ar 1 and Ar 2 are preferably both phenylene groups.
式（１）で表される芳香族スルホン酸誘導体の具体例としては、例えば下記の化合物が挙げられる。 Specific examples of the aromatic sulfonic acid derivative represented by the formula (1) include the following compounds.
また、上記化合物中、Ｘ１およびＸ２位の塩素原子やフッ素原子が他のハロゲン原子に置換された化合物や、Ａｒ１およびＡｒ２位のフェニレン基がそれぞれ独立したナフチレン基やビフェニレン基等の他の芳香族基に置換された化合物も用いることができる。
これらの化合物群の中でも、〔化４〕や〔化５〕に代表されるようなスルホン酸基であ
ることが特に好ましい。
Further, among the above compounds, compounds in which the chlorine atoms and fluorine atoms at the X 1 and X 2 positions are substituted with other halogen atoms, naphthylene groups and biphenylene groups in which the Ar 1 and Ar 2 position phenylene groups are independent, Compounds substituted with other aromatic groups can also be used.
Among these compound groups, sulfonic acid groups represented by [Chemical Formula 4] and [Chemical Formula 5] are particularly preferable.
上記式（１）で表される芳香族スルホン酸誘導体は、これをモノマー成分として用いて芳香族系高分子材料を調製する場合に、単独で用いても、２種以上を組み合わせて用いてもよい。 When the aromatic sulfonic acid derivative represented by the above formula (1) is used as a monomer component to prepare an aromatic polymer material, it may be used alone or in combination of two or more. Good.
（芳香族スルホン酸誘導体の製造方法）
上記式（１）で表される芳香族スルホン酸誘導体の製造方法としては、特に限定されるものではないが、例えば、下記の方法が挙げられる。
(Method for producing aromatic sulfonic acid derivative)
Although it does not specifically limit as a manufacturing method of the aromatic sulfonic acid derivative represented by the said Formula (1), For example, the following method is mentioned.
すなわち、当該誘導体は、下記式（２）で表される芳香族化合物から、還元反応にて水酸基を生成する第一反応工程と、第一反応工程で得られる反応生成物をスルホン化する第二反応工程とを経て製造することができる。 That is, the derivative includes a first reaction step for generating a hydroxyl group by a reduction reaction from an aromatic compound represented by the following formula (2), and a second sulfonating reaction product obtained in the first reaction step. It can manufacture through a reaction process.
[式（２）において、Ｘ１およびＸ２はそれぞれ独立した水素原子またはハロゲン原子を示す。] [In Formula (2), X 1 and X 2 each independently represent a hydrogen atom or a halogen atom. ]
式（２）で表される芳香族化合物の具体例としては、例えば、２,５−ジフェニル−１,４−ベンゾキノン、２,６−ジフェニル−１−４ベンゾキノン；３，６−ジフルオロ−２，５−ジフェニル−１，４−ベンゾキノン、３−フルオロ−２，５−ジフェニル−１，４−ベンゾキノン、３，５−ジフルオロ−２，６−ジフェニル−１，４−ベンゾキノン、３−フルオロ−２，６−ジフェニル−１，４−ベンゾキノン、５−フルオロ−２，６−ジフェニル−１，４−ベンゾキノンなどのハロゲン化誘導体；２,５−ジナフチル−１,４−ベンゾキノン、２,６−ジナフチル−１−４ベンゾキノン；３，６−ジフルオロ−２，５−ジナフチル−１，４−ベンゾキノン、３，５−ジフルオロ−２，６−ジナフチル−１，４−ベンゾキノンなどのナフチル基誘導体などが挙げられる。 Specific examples of the aromatic compound represented by the formula (2) include, for example, 2,5-diphenyl-1,4-benzoquinone, 2,6-diphenyl-1-4benzoquinone; 3,6-difluoro-2, 5-diphenyl-1,4-benzoquinone, 3-fluoro-2,5-diphenyl-1,4-benzoquinone, 3,5-difluoro-2,6-diphenyl-1,4-benzoquinone, 3-fluoro-2, Halogenated derivatives such as 6-diphenyl-1,4-benzoquinone and 5-fluoro-2,6-diphenyl-1,4-benzoquinone; 2,5-dinaphthyl-1,4-benzoquinone, 2,6-dinaphthyl-1 -4 benzoquinone; naphthyl group induction such as 3,6-difluoro-2,5-dinaphthyl-1,4-benzoquinone, 3,5-difluoro-2,6-dinaphthyl-1,4-benzoquinone Body and the like.
また、上記化合物中、Ｘ１およびＸ２位のフッ素原子が他のハロゲン原子に置換された化合物や、Ａｒ１およびＡｒ２位のフェニレン基がそれぞれ独立したナフチレン基やビフェニレン基等の他の芳香族基に置換された化合物も用いることができる。 In addition, among the above compounds, compounds in which the fluorine atoms at the X 1 and X 2 positions are substituted with other halogen atoms, and other aromatic compounds such as a naphthylene group or a biphenylene group in which the phenylene groups at the Ar 1 and Ar 2 positions are respectively independent. A compound substituted with a group can also be used.
上記式（２）で表される芳香族スルホン酸誘導体は、これをモノマー成分として用いて芳香族系高分子材料を調製する場合に、単独で用いても、２種以上を組み合わせて用いてもよい。 When the aromatic sulfonic acid derivative represented by the above formula (2) is used as a monomer component to prepare an aromatic polymer material, it may be used alone or in combination of two or more. Good.
第一反応工程において、還元反応は、通常触媒を用いて行われる。かかる触媒としては、一般に還元反応で用いられる触媒であれば特に限定されるものではなく、例えば、亜鉛末などの金属や水素化ホウ素ナトリウムなどの無機金属化合物などが挙げられる。 In the first reaction step, the reduction reaction is usually performed using a catalyst. Such a catalyst is not particularly limited as long as it is a catalyst generally used in a reduction reaction, and examples thereof include metals such as zinc dust and inorganic metal compounds such as sodium borohydride.
第一反応工程における還元反応は、その進行を適切に制御するため、溶媒中で行うことが好ましい。かかる溶媒としては、芳香族化合物が溶解し得る溶媒であること好ましく、例えば、テトラヒドロフラン、ジクロロメタン、クロロホルムなどが挙げられ、特にテトラヒドロフランを用いることが好ましい。これらの溶媒は、単独で用いても、２種以上を組み合わせても良い。 The reduction reaction in the first reaction step is preferably performed in a solvent in order to appropriately control the progress thereof. Such a solvent is preferably a solvent in which an aromatic compound can be dissolved, and examples thereof include tetrahydrofuran, dichloromethane, chloroform and the like, and tetrahydrofuran is particularly preferably used. These solvents may be used alone or in combination of two or more.
第一反応工程を溶媒中で行う場合、第一反応工程を経て得られる反応生成物の濃度が１質量％〜１０質量％となるように行うことが好ましい。濃度が１質量％未満の場合には、反応の進行が遅く、収率も低下する場合がある。濃度が１０質量％以上を超える場合には、副反応が進行する可能性もある。そのため、より好ましくは、３質量％〜７質量％である。 When performing a 1st reaction process in a solvent, it is preferable to carry out so that the density | concentration of the reaction product obtained through a 1st reaction process may be 1 mass%-10 mass%. When the concentration is less than 1% by mass, the progress of the reaction is slow, and the yield may be reduced. When the concentration exceeds 10% by mass or more, a side reaction may proceed. Therefore, More preferably, it is 3 mass%-7 mass%.
第一反応工程での反応温度は、―２０〜２００℃の範囲が好ましいが、用いる溶媒に順ずる。すなわち、還流操作にて反応を進行させるため、反応系中の温度は、用いた溶媒の沸点を超えることはない。例えば、溶媒にテトラヒドロフランを用いた場合は、沸点が６６℃であるため、その温度で反応を進行させることとなる。反応時間については、特に限定されるものではないが、反応中、発生する水素の発生がなくなった段階を反応終点とする。 The reaction temperature in the first reaction step is preferably in the range of −20 to 200 ° C., but conforms to the solvent used. That is, since the reaction proceeds by a reflux operation, the temperature in the reaction system does not exceed the boiling point of the solvent used. For example, when tetrahydrofuran is used as the solvent, since the boiling point is 66 ° C., the reaction proceeds at that temperature. The reaction time is not particularly limited, but the reaction end point is the stage at which no hydrogen is generated during the reaction.
第二反応工程は、上記第一反応工程を経て得られる反応生成物をスルホン化する工程であり、かかるスルホン化の方法としては特に限定されず、スルホン化剤の種類や量、反応温度および反応時間などを制御しながら反応生成物にスルホン化剤を反応させて、目的の芳香環にスルホン酸基を導入すればよい。 The second reaction step is a step of sulfonating the reaction product obtained through the first reaction step, and the sulfonation method is not particularly limited, and the type and amount of the sulfonating agent, the reaction temperature, and the reaction A sulfonic acid group may be introduced into the target aromatic ring by reacting the reaction product with a sulfonating agent while controlling time and the like.
第二反応工程で用いるスルホン化剤は、特に限定されるものではなく、例えば、硫酸、クロロスルホン酸、発煙硫酸、無水硫酸などが挙げられ、特に硫酸が好ましい。これらのスルホン化剤は単独で用いても、２種以上を組み合わせて用いてもよい。 The sulfonating agent used in the second reaction step is not particularly limited, and examples thereof include sulfuric acid, chlorosulfonic acid, fuming sulfuric acid, and anhydrous sulfuric acid, and sulfuric acid is particularly preferable. These sulfonating agents may be used alone or in combination of two or more.
第二反応工程は、０℃〜１００℃の範囲で行うことが好ましく、０℃〜５０℃の範囲で行うことがより好ましい。反応温度が０℃未満の場合には、スルホン化の終了までに時間がかかる場合がある。反応温度が５０℃を超える場合には、副生成物が多量に生成する場合がある。反応時間については、特に限定されるものではないが、出発原料が固体であるため、見た目にそれが溶解した段階を終点としている。 The second reaction step is preferably performed in the range of 0 ° C to 100 ° C, and more preferably performed in the range of 0 ° C to 50 ° C. When the reaction temperature is less than 0 ° C., it may take time to complete the sulfonation. When the reaction temperature exceeds 50 ° C., a large amount of by-products may be generated. The reaction time is not particularly limited, but since the starting material is solid, the end point is the stage where it is apparently dissolved.
第二反応工程において、スルホン化剤として硫酸を用いる場合には、硫酸の添加量は反応生成物に対して、２当量〜２０当量とすることが好ましく、２当量〜１０当量の範囲で行うことがより好ましい。スルホン化剤の添加量が２当量未満の場合には、反応生成物にスルホン酸基を十分に導入することができない。また、スルホン化剤が１０当量を超えて添加しても、スルホン酸基の導入効率が向上しない。 In the second reaction step, when sulfuric acid is used as the sulfonating agent, the amount of sulfuric acid added is preferably 2 to 20 equivalents, preferably 2 to 10 equivalents, relative to the reaction product. Is more preferable. When the addition amount of the sulfonating agent is less than 2 equivalents, sulfonic acid groups cannot be sufficiently introduced into the reaction product. Even if the sulfonating agent is added in an amount exceeding 10 equivalents, the introduction efficiency of the sulfonic acid group is not improved.
（芳香族系高分子材料）
本発明はモノマー（第一反応工程を経て得られた反応生成物）に対してスルホン化するものであり、フェニレン基を主鎖骨格とするポリマーに対してスルホン酸基を導入することを要しない。このため、本発明では、上記芳香族スルホン酸誘導体を用いて得られる芳香族高分子材料のスルホン化率を十分に上げることができる。
(Aromatic polymer materials)
The present invention sulfonates a monomer (reaction product obtained through the first reaction step), and does not require introduction of a sulfonic acid group into a polymer having a phenylene group as a main chain skeleton. . For this reason, in this invention, the sulfonation rate of the aromatic polymer material obtained using the said aromatic sulfonic acid derivative can fully be raised.
芳香族高分子材料は、例えば、上記芳香族スルホン酸誘導体の他に、芳香族ジハロゲン化物などを用いて、公知の方法（例えば、塩基性化合物の存在下、公知の芳香族求核置換反応による重合反応）で製造することができる。 The aromatic polymer material can be obtained by using a known method (for example, a known aromatic nucleophilic substitution reaction in the presence of a basic compound in addition to the above aromatic sulfonic acid derivative, using an aromatic dihalide). Polymerization reaction).
前記芳香族ジハロゲン化物としては、例えば４,４‘−ジフルオロジフェニルスルホン、２,６−ジフルオロベンゾニトリル、４,４‘−ジクロロジフェニルスルホンや２,６−ジクロロベンゾニトリルなどが挙げられる。 Examples of the aromatic dihalide include 4,4′-difluorodiphenylsulfone, 2,6-difluorobenzonitrile, 4,4′-dichlorodiphenylsulfone, and 2,6-dichlorobenzonitrile.
以下、実施例および比較例によって、本発明をより詳細に説明するが、本発明はこれらに限定されるものではなく、前記および後記の趣旨に適合し得る範囲で適宜変更して実施することが可能であり、それらはいずれも本発明の技術的範囲に包含される。なお下記実施例および比較例において「部」、「％」とあるのは、それぞれの重量部、質量％を意味する。 Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples. However, the present invention is not limited to these examples, and may be appropriately modified and implemented within a range that can meet the above and the gist. All of these are possible within the scope of the present invention. In the following examples and comparative examples, “parts” and “%” mean parts by weight and mass%, respectively.
（実施例１）芳香族スルホン酸誘導体１の合成
＜第一反応工程＞
還流管および攪拌機を取り付けた三口フラスコに芳香族炭化水素化合物として、２,５−ジフェニル−１,４−ベンゾキノン２０．０ｇ（７６．８ｍｍｏｌ）、溶媒としてテトラヒドロフラン４００ｍｌ、および触媒として亜鉛末５０.０ｇ（７６５ｍｍｏｌ）を入れ、加熱還流した。還流開始後、あらかじめ取り付けておいた滴下漏斗より塩酸６０ｍｌを少しずつ滴下し、無くなるまで滴下を続けた。溶液が中性になるまで反応を続けた。反応後、亜鉛残渣をろ過にて取り除き、ろ液を溶媒留去にて白色固体を得た。この白色固体を酢酸エチル３００ｍｌに溶解させ、そこに水を１００ｍｌ注ぎ有機層を洗浄した。この操作を３回繰り返した。有機層を硫酸ナトリウムにて乾燥後、ろ過してろ液を回収、次いで溶媒留去し白色固体を得た。最後に、トルエンにて再結晶化し、２０．１ｇの反応生成物を得た。
Example 1 Synthesis of Aromatic Sulfonic Acid Derivative 1 <First Reaction Step>
In a three-necked flask equipped with a reflux tube and a stirrer, 20.0 g (76.8 mmol) of 2,5-diphenyl-1,4-benzoquinone as an aromatic hydrocarbon compound, 400 ml of tetrahydrofuran as a solvent, and 50.0 g of zinc powder as a catalyst (765 mmol) was added and heated to reflux. After the start of reflux, 60 ml of hydrochloric acid was dropped little by little from a dropping funnel attached in advance, and the dropping was continued until it disappeared. The reaction was continued until the solution was neutral. After the reaction, the zinc residue was removed by filtration, and the filtrate was evaporated to obtain a white solid. This white solid was dissolved in 300 ml of ethyl acetate, and 100 ml of water was poured therein to wash the organic layer. This operation was repeated three times. The organic layer was dried over sodium sulfate and filtered to collect the filtrate, and then the solvent was distilled off to obtain a white solid. Finally, it was recrystallized with toluene to obtain 20.1 g of a reaction product.
＜第二反応工程＞
攪拌機を取り付けた三口フラスコに、得られた反応生成物１０．０ｇ（３８．１ｍｍｏｌ）を入れ、０℃に冷却したのち、濃硫酸５０ｍｌ（１８ｍｏｌ／ｌ）を加えて、攪拌させた。完全に溶解したことを確認した後、室温に戻しさらに１時間攪拌を継続した。攪拌後、２００ｇの氷中に溶液を注ぎ、攪拌しながら、その中に塩化ナトリウムを加えて塩析操作を行った。析出してきた固体をろ過にて回収し、固体を純水にて再結晶化し、下記構造式で表される芳香族スルホン酸誘導体１を１４．２ｇ得た。
<Second reaction step>
Into a three-necked flask equipped with a stirrer, 10.0 g (38.1 mmol) of the obtained reaction product was put, and after cooling to 0 ° C., 50 ml of concentrated sulfuric acid (18 mol / l) was added and stirred. After confirming complete dissolution, the temperature was returned to room temperature and stirring was continued for another hour. After stirring, the solution was poured into 200 g of ice, and while stirring, sodium chloride was added thereto for salting out. The precipitated solid was collected by filtration, and the solid was recrystallized with pure water to obtain 14.2 g of an aromatic sulfonic acid derivative 1 represented by the following structural formula.
当該芳香族スルホン酸誘導体１の１Ｈ−ＮＭＲスペクトルを図１に、１３Ｃ−ＮＭＲスペクトルを図２に示す。 The 1 H-NMR spectrum of the aromatic sulfonic acid derivative 1 is shown in FIG. 1, and the 13 C-NMR spectrum is shown in FIG.
なお、１Ｈ−ＮＭＲ測定および１３Ｃ−ＮＭＲ測定の条件は以下の通りである。
［１Ｈ−ＮＭＲ条件］
装置：ＶＡＲＩＡＮ社製ＮＭＲ装置 ４００−ＭＲ
共鳴周波数：４００ＭＨｚ
測定溶媒：ＤＭＳＯ−ｄ６
試料溶液濃度：２０ｍｇ／ｍｌ
積算回数：３２回
測定温度：室温
The conditions for 1 H-NMR measurement and 13 C-NMR measurement are as follows.
[ 1 H-NMR conditions]
Apparatus: NMR apparatus 400-MR manufactured by VARIAN
Resonance frequency: 400 MHz
Measuring solvent: DMSO-d6
Sample solution concentration: 20 mg / ml
Integration count: 32 times Measurement temperature: room temperature
［１３Ｃ−ＮＭＲ条件］
装置：ＶＡＲＩＡＮ社製ＮＭＲ装置 ４００−ＭＲ
共鳴周波数：４００ＭＨｚ
測定溶媒：ＤＭＳＯ−ｄ６
試料溶液濃度：２０ｍｇ／ｍｌ
積算回数：２５６回
測定温度：室温
[ 13C -NMR conditions]
Apparatus: NMR apparatus 400-MR manufactured by VARIAN
Resonance frequency: 400 MHz
Measuring solvent: DMSO-d6
Sample solution concentration: 20 mg / ml
Integration count: 256 times Measurement temperature: room temperature
［溶液粘度］
ポリマー粉末を０．５ｇ／ｄＬの濃度でＮ−メチル−２−ピロリドンに溶解し、３０℃の恒温槽中でウベローデ型粘度計を用いて粘度測定を行い、対数粘度（ｌｎ［ｔａ／ｔｂ］）／ｃで評価した（ｔａは試料溶液の落下秒数、ｔｂは溶媒のみの落下秒数、ｃはポリマー濃度を表す）。
[Solution viscosity]
The polymer powder was dissolved in N-methyl-2-pyrrolidone at a concentration of 0.5 g / dL, the viscosity was measured using a Ubbelohde viscometer in a thermostatic bath at 30 ° C., and the logarithmic viscosity (ln [ta / tb] ) / C (ta represents the sample solution dropping time, tb represents the solvent dropping time, and c represents the polymer concentration).
（実施例２）芳香族スルホン酸誘導体２の合成
実施例１において、２,５−ジフェニル−１,４−ベンゾキノンの代わりに、２，６−ジフェニル１，４−ベンゾキノンを用いた以外は実施例１と同様にて下記構造式で表される芳香族スルホン酸誘導体２を得た。
(Example 2) Synthesis of aromatic sulfonic acid derivative 2 In Example 1, except that 2,6-diphenyl-1,4-benzoquinone was used instead of 2,5-diphenyl-1,4-benzoquinone, Example As in Example 1, an aromatic sulfonic acid derivative 2 represented by the following structural formula was obtained.
（実施例３）芳香族スルホン酸誘導体３の合成
実施例１において、２,５−ジフェニル−１,４−ベンゾキノンの代わりに、３，６−ジフルオロ−２，５−ジフェニル１，４−ベンゾキノンを用いた以外は実施例１と同様にて下記構造式で表される芳香族スルホン酸誘導体３を得た。
(Example 3) Synthesis of aromatic sulfonic acid derivative 3 In Example 1, 3,6-difluoro-2,5-diphenyl 1,4-benzoquinone was used instead of 2,5-diphenyl-1,4-benzoquinone. An aromatic sulfonic acid derivative 3 represented by the following structural formula was obtained in the same manner as in Example 1 except that it was used.
（参考例）芳香族系高分子材料の調製
実施例１で合成した芳香族スルホン酸誘導体１を用いて、以下の方法にしたがって芳香族高分子材料を調製した。
(Reference Example) Preparation of Aromatic Polymer Material Using the aromatic sulfonic acid derivative 1 synthesized in Example 1, an aromatic polymer material was prepared according to the following method.
ジフルオロベンゾニトリル２．７ｇ、炭酸カリウム２．９８ｇ、ジメチルスルホキシド６１．０ｍｌ、およびトルエン３０．５ｍｌをフラスコに入れ、窒素雰囲気下、攪拌しながら１４０℃に昇温し、トルエンを留去した。その後、上記スルホン酸誘導体１を１０ｇ系内に加え、１６０℃で１０時間攪拌した。得られた溶液をアセトン中に滴下し、析出物を回収し、乾燥させて、下記式で表される芳香族高分子材料１１．８ｇを得た。当該材料を０．５ｇ／ｄＬの濃度でＮ−メチルピロリドンに溶解し、３０℃の恒温槽中でウベローデ型粘度計を用いて粘度測定を行ったところ、対数粘度は、０．１８ｄＬ／ｇであった。 2.7 g of difluorobenzonitrile, 2.98 g of potassium carbonate, 61.0 ml of dimethyl sulfoxide, and 30.5 ml of toluene were placed in a flask, heated to 140 ° C. with stirring in a nitrogen atmosphere, and toluene was distilled off. Thereafter, 10 g of the sulfonic acid derivative 1 was added to the system and stirred at 160 ° C. for 10 hours. The obtained solution was dropped into acetone, and the precipitate was collected and dried to obtain 11.8 g of an aromatic polymer material represented by the following formula. The material was dissolved in N-methylpyrrolidone at a concentration of 0.5 g / dL, and the viscosity was measured using a Ubbelohde viscometer in a constant temperature bath at 30 ° C. The logarithmic viscosity was 0.18 dL / g. there were.
本発明の芳香族スルホン酸誘導体は、プロトン伝導性に優れる芳香族系高分子材料、および該高分子材料を得るためのモノマーを提供することができ、固体高分子型燃料電池等に好適に利用できるため産業上の寄与は大である。 The aromatic sulfonic acid derivative of the present invention can provide an aromatic polymer material excellent in proton conductivity and a monomer for obtaining the polymer material, and is suitably used for a solid polymer fuel cell and the like. Because it can, the industrial contribution is significant.
Claims (6)
[式（１）において、Ｘ１およびＸ２はそれぞれ独立した水素原子またはハロゲン原子を示す。Ｒは水素原子、アルカリ金属原子、アルカリ土類金属原子、または炭素数１〜２０の炭化水素基、ａおよびｂはそれぞれ独立した１以上の整数、Ａｒ１およびＡｒ２は独立した芳香族基を示す。] An aromatic sulfonic acid derivative represented by the following formula (1)
[In Formula (1), X 1 and X 2 each independently represent a hydrogen atom or a halogen atom. R represents a hydrogen atom, an alkali metal atom, an alkaline earth metal atom, or a hydrocarbon group having 1 to 20 carbon atoms, a and b each represent an independent integer of 1 or more, and Ar 1 and Ar 2 represent an independent aromatic group. Show. ]
[式（２）において、Ｘ１およびＸ２はそれぞれ独立した水素原子またはハロゲン原子を示す。] It is a manufacturing method of the aromatic sulfonic acid derivative as described in any one of Claim 1 to 2, Comprising: The 1st reaction which produces | generates a hydroxyl group by the reductive reaction from the aromatic compound represented by following formula (2). A process for producing an aromatic sulfonic acid derivative, comprising a step and a second reaction step of sulfonating the reaction product obtained in the first reaction step.
[In Formula (2), X 1 and X 2 each independently represent a hydrogen atom or a halogen atom. ]
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018160618A1 (en) * | 2017-02-28 | 2018-09-07 | Wisconsin Alumni Research Foundation | High-and low-potential, water-soluble, robust quinones |
| US10597359B2 (en) | 2017-02-28 | 2020-03-24 | Wisconsin Alumni Research Foundation | High-solubility thioether quinones |
| CN111051382A (en) * | 2017-07-06 | 2020-04-21 | 莫西聚合物公司 | Polymer comprising sulfonated 2, 6-diphenyl-1, 4-phenylene ether repeat units |
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2010
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018160618A1 (en) * | 2017-02-28 | 2018-09-07 | Wisconsin Alumni Research Foundation | High-and low-potential, water-soluble, robust quinones |
| US10597359B2 (en) | 2017-02-28 | 2020-03-24 | Wisconsin Alumni Research Foundation | High-solubility thioether quinones |
| CN111051382A (en) * | 2017-07-06 | 2020-04-21 | 莫西聚合物公司 | Polymer comprising sulfonated 2, 6-diphenyl-1, 4-phenylene ether repeat units |
| US11434329B2 (en) * | 2017-07-06 | 2022-09-06 | Mxpolymers B.V. | Polymers comprising sulfonated 2,6-diphenyl-1,4-phenylene oxide repeating units |
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